WO2020248567A1 - Électrolyte de batterie secondaire au lithium-ion pour réduire la résistance de batterie et batterie secondaire au lithium-ion correspondante - Google Patents

Électrolyte de batterie secondaire au lithium-ion pour réduire la résistance de batterie et batterie secondaire au lithium-ion correspondante Download PDF

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WO2020248567A1
WO2020248567A1 PCT/CN2019/127033 CN2019127033W WO2020248567A1 WO 2020248567 A1 WO2020248567 A1 WO 2020248567A1 CN 2019127033 W CN2019127033 W CN 2019127033W WO 2020248567 A1 WO2020248567 A1 WO 2020248567A1
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carbonate
lithium
electrolyte
secondary battery
lithium secondary
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PCT/CN2019/127033
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English (en)
Chinese (zh)
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范伟贞
曹哥尽
范超君
余乐
赵经纬
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广州天赐高新材料股份有限公司
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Priority to EP19933122.4A priority Critical patent/EP3972024A4/fr
Priority to US17/614,215 priority patent/US20220238909A1/en
Publication of WO2020248567A1 publication Critical patent/WO2020248567A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of lithium secondary batteries. More specifically, the present invention provides a lithium secondary battery electrolyte and a lithium secondary battery that reduce battery impedance.
  • lithium secondary batteries Because of its high energy density, long cycle life, and pollution-free characteristics, lithium secondary batteries have broad application prospects in consumer electronics, power car batteries and energy storage power supplies.
  • lithium secondary battery technology applied to automobile power has developed rapidly. Higher requirements are put forward on the performance of lithium secondary batteries.
  • the battery needs to have a longer service life, needs to be able to be used under extreme temperatures, needs to be able to charge and discharge quickly (high rate), and needs to have better safety.
  • the battery pack of an electric vehicle is generally composed of multiple batteries in series or in parallel.
  • the battery generates a certain amount of heat during normal operation.
  • the entire battery pack uses a battery thermal management system to conduct thermal management of the battery.
  • the greater the discharge rate of the battery or the greater the internal resistance of the battery the greater the heat generation of the battery. If the internal resistance of the battery can be reduced, the heat generation of the battery can be reduced. At the same time, the higher the charge and discharge rate of the battery, the greater the heat generation of the battery. If the internal resistance of the battery can be reduced, the heat generation of the battery with high charge and discharge rate can also be reduced.
  • the battery pack is composed of multiple batteries, the consistency of a single battery determines the service life of the entire battery pack. If the impedance of the battery can be reduced, the consistency of the battery can be greatly improved, thereby increasing the service life of the battery.
  • the first aspect of the present invention provides an electrolyte for a lithium secondary battery, which contains a non-aqueous solvent, a lithium salt and an additive; wherein the additive includes a sulfonate compound.
  • R 1 and R 2 are independently selected from one of aliphatic hydrocarbon groups with 1-5 carbon atoms, aryl groups, alkyl-substituted aryl groups, and silicon groups; any group can be substituted by halogen atoms .
  • R 1 and R 2 are each independently selected from methyl, ethyl, propyl, fluoromethyl, fluoroethyl, vinyl, allyl, phenyl, benzene One of methyl, fluorophenyl, trimethylsilyl, and trivinylsilyl.
  • the sulfonate compound is selected from Any one or a combination of multiple.
  • the mass of the sulfonate compound accounts for 0.1% to 5% of the total mass of the electrolyte.
  • the additive further includes a second additive selected from the group consisting of vinylene carbonate, fluoroethylene carbonate, lithium difluorophosphate, lithium dioxalate borate, and difluorooxalic acid Lithium borate, 1,3-propane sultone, triallyl isocyanurate, methylene disulfonate, vinyl sulfate, triallyl phosphate, tripropynyl phosphate, three Any one or a combination of (trimethylsilane) phosphate and tris(trimethylsilane) borate.
  • a second additive selected from the group consisting of vinylene carbonate, fluoroethylene carbonate, lithium difluorophosphate, lithium dioxalate borate, and difluorooxalic acid Lithium borate, 1,3-propane sultone, triallyl isocyanurate, methylene disulfonate, vinyl sulfate, triallyl phosphate, tripropynyl
  • the mass of the second additive accounts for 0.01% to 10% of the total mass of the electrolyte.
  • the mass of the non-aqueous solvent accounts for 67-91% of the total mass of the electrolyte.
  • the non-aqueous solvent includes cyclic ester and chain ester.
  • the cyclic ester is selected from any one or a combination of ethylene carbonate, propylene carbonate, butylene carbonate, and ⁇ -butyrolactone.
  • the chain ester is selected from dimethyl carbonate, diethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, carbonic acid Ethylene propyl, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, 2,2-difluoroethyl Any one or a combination of glycyl acetate.
  • the mass of the lithium salt accounts for 8-18% of the total mass of the electrolyte.
  • the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium bisfluorosulfonimide, and lithium bis(trifluoromethanesulfonyl)imide.
  • the second aspect of the present invention provides a lithium secondary battery, which includes a positive electrode, a negative electrode, and an electrolyte; wherein the electrolyte used is the electrolyte.
  • the lithium secondary battery is selected from any one of lithium ion batteries, lithium sulfur batteries, and lithium air batteries.
  • the active material of the positive electrode is a lithium-containing transition metal oxide and/or a lithium-containing transition metal phosphate compound.
  • the active material of the positive electrode is selected from Li 1+a (Ni x Co y M 1-xy )O 2 , Li(Ni n Mn m Co 2-nm )O 4 , LiM Any of p (PO 4 ) q ; where 0 ⁇ a ⁇ 0.3, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ x+y ⁇ 1, 0 ⁇ n ⁇ 2, 0 ⁇ m ⁇ 2, 0 ⁇ n+m ⁇ 2, M is selected from any one of Al, Fe, Ni, Co, Mn, and V, and 0 ⁇ p ⁇ 5, 0 ⁇ q ⁇ 5.
  • the active material of the negative electrode is selected from any one or a combination of lithium metal, lithium alloy, carbon material, silicon or tin and oxides thereof.
  • the present invention Compared with the prior art, the present invention has the following beneficial effects: the present invention provides an electrolyte for lithium secondary batteries.
  • the lithium secondary battery using the electrolyte has lower impedance, and at the same time has better low-temperature performance, High temperature performance and cycle life; at the same time, the present invention also discloses the use of lithium ion batteries containing the electrolyte.
  • the first aspect of the present invention provides an electrolyte for a lithium secondary battery, which contains a non-aqueous solvent, a lithium salt and an additive; wherein the additive includes a sulfonate compound.
  • the sulfonate compound is selected from at least one compound represented by the general formula (A):
  • R 1 and R 2 are independently selected from one of aliphatic hydrocarbon groups with 1-5 carbon atoms, aryl groups, alkyl-substituted aryl groups, and silicon groups; any group can be substituted by halogen atoms .
  • Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, new Pentyl, 1-methylbutyl, 2-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, etc.
  • alkyl groups substituted by halogen atoms include fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 1, 2-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1-fluoro-n-propyl, 2-fluoro-n-propyl, 3-fluoro-n-propyl Propyl, 1,1-difluoro-n-propyl, 1,2-difluoro-n-propyl, 1,3-difluoro-n-propyl, 2,2-difluoro-n-propyl, 2,3-difluoro-n-propyl Propyl, 3,3-difluoro-n-propyl, 3,3,3-trifluoro-n-propyl, 2,2,3,3,3,
  • alkenyl groups include alkenyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2- Pentenyl, 3-pentenyl, 4-pentenyl and the like.
  • alkenyl groups substituted with halogen atoms include 1-fluorovinyl, 2-fluorovinyl, 1,2-difluorovinyl, 2,2-difluorovinyl, 1,2,2-trifluoroethylene, Fluorovinyl, 1-fluoro-1-propenyl, 2-fluoro-1-propenyl, 3-fluoro-1-propenyl, 1,2-difluoro-1-propenyl, 1,3-difluoro- 1-propenyl, 2,3-difluoro-1-propenyl, 3,3-difluoro-1-propenyl, 1,2,3-trifluoro-1-propenyl, 1,3,3-tri Fluoro-1-propenyl, 2,3,3-trifluoro-1-propenyl, 3,3,3-trifluoro-1-propenyl, 1,2,3,3-tetrafluoro-1-propenyl , 1,3,3,3-tetrafluoro-1-prop
  • alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl Alkynyl, 3-pentynyl, 4-pentynyl and the like.
  • alkynyl groups substituted by halogen atoms include 2-fluoroethynyl, 3-fluoro-1-propynyl, 3,3-difluoro-1-propynyl, and 3,3,3-trifluoro -1-propynyl, 3-fluoro-2-propynyl, 1-fluoro-2-propynyl, 1,1-difluoro-2-propynyl, 1,3-difluoro-2-propynyl Alkynyl, 1,1,3-trifluoro-2-propynyl, etc.
  • aryl groups include phenyl, tolyl, xylyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, isobutyl Phenyl, tert-butylphenyl, etc.
  • phenyl substituted by alkyl examples include benzyl, ⁇ -methylbenzyl, 1-methyl-1-phenylethyl, phenethyl, 2-phenylpropyl, 2-methyl -2-phenylpropyl, 3-phenylpropyl, 3-phenylbutyl, 3-methyl-3-phenylbutyl, 4-phenylbutyl, 5-phenylpentyl, 6- Phenylhexyl and others.
  • Examples of the phenyl substituted by halogen atoms include: 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2 ,5-Difluorophenyl, 2,6-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,5,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4, 5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,4,5,6-tetrafluorophenyl, pentafluorophenyl.
  • R 1 and R 2 are each independently selected from methyl, ethyl, propyl, fluoromethyl, fluoroethyl, vinyl, propenyl, phenyl, tolyl, fluoro One of phenyl, trimethylsilyl, trivinyl, and silicon.
  • sulfonate compound more preferably Any one or a combination of multiple.
  • the mass of the sulfonate compound accounts for 0.1% to 5% of the total mass of the electrolyte; more preferably, the mass of the sulfonate compound accounts for 0.5% to 5% of the total mass of the electrolyte.
  • the additive further includes a second additive.
  • a carbonate compound having a carbon-carbon unsaturated bond As the second additive, a carbonate compound having a carbon-carbon unsaturated bond, a carbonate compound having a halogen atom, a fluorophosphoric acid compound, a phosphoric acid ester compound, a silicon-containing compound, a sulfonic acid ester compound, a sulfate ester compound, Compounds having isocyanate groups, etc.
  • carbonate compound having a carbon-carbon unsaturated bond as long as it is a carbonate having a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, there are no other restrictions, and any unsaturated carbonate can be used.
  • carbonates having an aromatic ring are also included in carbonates having an unsaturated bond.
  • carbonate compounds having carbon-carbon unsaturated bonds include methyl vinyl carbonate, ethyl vinyl carbonate, divinyl carbonate, methyl propynyl carbonate, and ethyl propyne carbonate.
  • carbonate compounds having halogen atoms include fluoroethylene carbonate, chloroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4,4 -Dichloroethylene carbonate, 4,5-dichloroethylene carbonate, 4-fluoro-4-methylethylene carbonate, 4-chloro-4-methylethylene carbonate, 4,5-di Fluoro-4-methylethylene carbonate, 4,5-dichloro-4-methylethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4-chloro-5-methylethylene carbonate Ethyl ester, 4,4-difluoro-5-methylethylene carbonate, 4,4-dichloro-5-methylethylene carbonate, 4-(fluoromethyl)ethylene carbonate, 4-( Chloromethyl) ethylene carbonate, 4-(difluoromethyl) ethylene carbonate, 4-(dichloromethyl) ethylene carbonate, 4-(trifluoromethyl) ethylene carbonate, 4- (Trichloromethyl) ethylene carbonate
  • fluoromethyl phenyl carbonate 2-fluoroethyl phenyl carbonate, 2,2-difluoroethyl phenyl carbonate, 2,2,2-trifluoroethyl phenyl carbonate , Chloromethylphenyl carbonate, 2-chloroethylphenyl carbonate, 2,2-dichloroethylphenyl carbonate, 2,2,2-trichloroethylphenyl carbonate, fluoromethyl carbonate Vinyl vinyl ester, 2-fluoroethyl vinyl carbonate, 2,2-difluoroethyl vinyl carbonate, 2,2,2-trifluoroethyl vinyl carbonate, chloromethyl vinyl carbonate , 2-chloroethyl vinyl carbonate, 2,2-dichloroethyl vinyl carbonate, 2,2,2-trichloroethyl vinyl carbonate, fluoromethyl allyl carbonate, 2 -Fluoroethyl allyl ester, 2,2-
  • fluorophosphoric acid compound examples include: lithium difluorophosphate, difluorophosphoric acid, monofluorophosphoric acid, methyl difluorophosphate, ethyl difluorophosphate, dimethyl fluorophosphate, diethyl fluorophosphate, difluoro-difluorophosphate Lithium oxalate phosphate, lithium tetrafluorooxalate phosphate, lithium trioxalate phosphate, lithium difluorooxalate borate, lithium dioxalate borate, etc.
  • Examples of phosphoric acid ester compounds include: dimethyl vinyl phosphate, diethyl vinyl phosphate, dipropyl vinyl phosphate, dibutyl vinyl phosphate, and dipentyl vinyl phosphate.
  • Vinyl compound dimethyl vinyl phosphate, diethyl vinyl phosphate, dipropyl vinyl phosphate, dibutyl vinyl phosphate, and dipentyl vinyl phosphate.
  • Phosphoric acid 2-acryloxy methyl dimethyl ester Phosphoric acid 2-acryloxy methyl dimethyl ester, phosphoric acid 2-acryloxy methyl diethyl ester, phosphoric acid 2-acryloxy methyl dipropyl ester, phosphoric acid 2-acryloxy methyl ester 2-acryloxymethyl compounds such as dibutyl phosphate and 2-acryloxymethyl dipentyl phosphate;
  • Phosphoric acid 2-acryloyloxyethyl dimethyl ester Phosphoric acid 2-acryloyloxyethyl diethyl ester, Phosphoric acid 2-acryloyloxyethyl dipropyl ester, Phosphoric acid 2-acryloyloxy ethyl 2-acryloyloxyethyl compounds such as dibutyl phosphate and 2-acryloyloxyethyl dipentyl phosphate;
  • Diallyl methyl phosphate, diallyl ethyl phosphate, diallyl phosphate, diallyl butyl phosphate, diallyl pentyl phosphate, etc. have allyl groups Compound
  • Dipropargyl methyl phosphate, dipropargyl ethyl phosphate, dipropargyl propyl phosphate, dipropargyl butyl phosphate and dipropargyl pentyl phosphate, etc. have propargyl groups Compound
  • Bis(2-acryloyloxymethyl)methyl phosphate bis(2-acryloyloxymethyl)ethyl phosphate, bis(2-acryloyloxymethyl)propyl phosphate, bis(2-acryloyloxymethyl)propyl phosphate, double phosphate
  • 2-acryloxymethyl groups such as (2-acryloyloxymethyl)butyl ester and bis(2-acryloyloxymethyl)pentyl phosphate;
  • Trivinyl phosphate Trivinyl phosphate, triallyl phosphate, tripropargyl phosphate, tris(2-acryloyloxymethyl) phosphate, tris(2-acryloyloxyethyl) phosphate, etc.
  • silicon-containing compounds include: tris(trimethylsilyl) phosphate, bis(trimethylsilyl) phosphate, mono(trimethylsilyl) phosphate, dimethyl tris Methyl silyl ester, methyl bis(trimethylsilyl) phosphate, diethyltrimethylsilyl phosphate, ethyl bis(trimethylsilyl) phosphate, dipropylene phosphate Trimethylsilyl phosphate, propyl bis(trimethylsilyl) phosphate, dibutyltrimethylsilyl phosphate, butyl bis(trimethylsilyl) phosphate, phosphoric acid Dioctyl trimethylsilyl ester, octyl bis(trimethylsilyl) phosphate, diphenyl trimethylsilyl phosphate, phenyl bis(trimethylsilyl) phosphate , Bis(trifluoroethyl)(trimethylsilyl) phosphate, trifluoroe
  • Tris(trimethylsilane) borate tris(trimethoxysilyl) borate, tris(triethylsilyl) borate, tris(triethoxysilyl) borate, tris borate (Dimethylvinylsilyl) and boric acid compounds such as tris(diethylvinylsilyl) borate;
  • Sulfonic acid compounds such as trimethylsilyl methanesulfonate and trimethylsilyl tetrafluoromethanesulfonate.
  • sulfonate compounds include: 1,3-propane sultone, 1-fluoro-1,3-propane sultone, 2-fluoro-1,3-propane sultone, 3- Fluoro-1,3-propane sultone, 1-methyl-1,3-propane sultone, 2-methyl-1,3-propane sultone, 3-methyl-1,3 -Propylene sultone, 1-propene-1,3-sultone, 2-propene-1,3-sultone, 1-fluoro-1-propene-1,3-sultone, 2-fluoro-1-propene-1,3-sultone, 3-fluoro-1-propene-1,3-sultone, 1-fluoro-2-propene-1,3-sultone , 2-fluoro-2-propene-1,3-sultone, 3-fluoro-2-propene-1,3-sultone, 1-methyl-1-propene-1,3-sulf
  • sulfate compounds include 1,2-ethylene glycol sulfate, 1,2-propanediol sulfate, 1,3-propanediol sulfate, 1,2-butanediol sulfate, 1,3-butane Glycol sulfate, 1,4-butanediol sulfate, 1,2-pentanediol sulfate, 1,3-pentanediol sulfate, 1,4-pentanediol sulfate and 1,5-pentane Glycol sulfate, ethylene sulfite, propylene sulfite, ethylene sulfate, propylene sulfate, butylene sulfate, hexylene sulfate, vinylene sulfate, 3-sulfolene, diethylene Base sulfone, dimethyl sulfate, diethyl s
  • Examples of compounds having isocyanate groups include: methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, vinyl Isocyanate, allyl isocyanate, triallyl isocyanurate, ethynyl isocyanate, propynyl isocyanate, phenyl isocyanate, fluorophenyl isocyanate.
  • the second additive is selected from vinylene carbonate, fluoroethylene carbonate, lithium difluorophosphate, lithium dioxalate borate, lithium difluorooxalate borate, 1,3-propane sultone, triallyl iso Cyanurate, methylene methane disulfonate, vinyl sulfate, triallyl phosphate, tripropynyl phosphate, tris(trimethylsilane) phosphate, tris(trimethylsilane) boric acid Any one or a combination of esters.
  • the second additive is selected from vinylene carbonate, fluoroethylene carbonate, lithium difluorophosphate, lithium difluorooxalate borate, triallyl isocyanurate, triallyl phosphate, tripropylene Any one or a combination of alkynyl phosphates.
  • the mass of the second additive accounts for 0.01% to 10% of the total mass of the electrolyte; preferably, the mass of the second additive accounts for 0.1% to 8% of the total mass of the electrolyte; more preferably, the mass of the second additive accounts for 0.5% of the total mass of the electrolyte. % ⁇ 5.5%.
  • the mass of the non-aqueous solvent accounts for 67 to 91% of the total mass of the electrolyte; preferably, the mass of the non-aqueous solvent accounts for 77 to 87% of the total mass of the electrolyte.
  • non-aqueous solvent various non-aqueous solvents can be appropriately selected, and it is preferable to use at least one selected from a cyclic aprotic solvent and a chain aprotic solvent to improve the solubility, stability and Electrical conductivity.
  • cyclic aprotic solvent cyclic esters, cyclic sulfones, and cyclic ethers can be used.
  • cyclic sulfones include, but are not limited to, sulfolane, 2-methyl sulfolane, 3-methyl sulfolane, dimethyl sulfone, diethyl sulfone, dipropyl sulfone, methyl ethyl sulfone, methyl propyl sulfone Sulfone etc.
  • cyclic ethers include but are not limited to dioxolane.
  • cyclic esters include cyclic carbonates and cyclic carboxylic acid esters.
  • the type of cyclic carbonate is not limited, including but not limited to: methyl vinyl carbonate, ethyl vinyl carbonate, divinyl carbonate, methallyl carbonate, ethyl allyl Carbonate, diallyl carbonate, methyl propynyl carbonate, ethyl propynyl carbonate, dipropynyl carbonate, methyl phenyl carbonate, ethyl phenyl carbonate, diphenyl carbonate, etc.
  • Chain carbonates vinylene carbonate, methyl vinylene carbonate, 4,4-dimethyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, vinyl ethylene carbonate , 4,4-divinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, allyl ethylene carbonate, 4,4-diallyl ethylene carbonate, 4,5-diallyl ethylene carbonate, methylene ethylene carbonate, 4,4-dimethyl-5-methylene ethylene carbonate, ethynyl ethylene carbonate, 4,4-diethynyl ethylene carbonate, 4,5-diethynyl ethylene carbonate, propynyl ethylene carbonate, 4,4-dipropynyl ethylene carbonate, 4 , 5-Dipropynyl ethylene carbonate, phenyl ethylene carbonate, 4,5-diphenyl ethylene carbonate, phenylene carbonate, fluorocarbonic acid, fluoroethylene carbonate, Trifluoroethylene carbon
  • the types of cyclic carboxylic acid esters are not limited, including but not limited to: ⁇ -butyrolactone, methyl ⁇ -butyrolactone, ethyl ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexyl Lactone, ⁇ -heptanolide, ⁇ -valerolactone, ethyl ⁇ -valerolactone, etc.
  • the cyclic ester is preferably at least one of ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, and butylene carbonate.
  • chain aprotic solvent chain esters, chain ethers, etc. can be used.
  • chain esters examples include cyclic carbonates, cyclic carboxylic acid esters, and chain phosphate esters.
  • chain carboxylic acid esters are not limited, including but not limited to: dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl methyl carbonate, methyl acetate, ethyl acetate, Propyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, trimethyl methyl acetate, trimethyl ethyl acetate, methyl malonate, ethyl malonate, methyl succinate Ester, ethyl succinate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethylene glycol diacetate, propylene glycol diacetate, 2,2-difluoroethyl Acetate etc.
  • chain carbonates are not limited, including but not limited to: dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethylene propyl carbonate, dipropyl carbonate, two Ethyl carbonate and so on.
  • the type of chain phosphate is not limited, including but not limited to: trimethyl phosphate, triethyl phosphate, triphenyl phosphate and the like.
  • dimethyl carbonate, diethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethylene propyl carbonate, methyl formate, and ethyl formate are preferred.
  • the weight ratio of the cyclic ester and the chain ester is 1:(1-5); preferably, in one embodiment, the weight ratio of the cyclic ester and the chain ester is 1:( 1 ⁇ 2.5).
  • the electrolyte used in the non-aqueous electrolyte solution of the present invention is not limited, and any known electrolyte can be used as long as it is used as an electrolyte in the target non-aqueous electrolyte secondary battery.
  • a lithium salt is generally used as an electrolyte.
  • lithium salts include inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiAlF 4 , LiSbF 6 , LiTaF 6 , and LiWF 7 ; lithium tungstates such as LiWOF 5 ; HCO 2 Li, CH 3 CO 2 Li , CH 2 FCO 2 Li, CHF 2 CO 2 Li, CF 3 CO 2 Li, CF 3 CH 2 CO 2 Li, CF 3 CF 2 CO 2 Li, CF 3 CF 2 CF 2 CO 2 Li, CF 3 CF 2 CF 2 CO 2 Li and other carboxylic acid lithium salts; FSO 3 Li, CH 3 SO 3 Li, CH 2 FSO 3 Li, CHFSO 3 Li, CHF 2 SO 3 Li, CF 3 SO 3 Li, CF 3 CF 2 SO 3 Li, CF 3 CF 2 CF 2 SO 3 Li, CF 3 CF 2 CF 2 SO 3 Li, CF 3 CF 2 CF 2 SO 3 Li and other sulfonic acid lithium salts
  • the lithium salt is preferably at least one of LiSbF 6 , lithium bisfluorosulfonimide, and lithium bis(trifluoromethanesulfonyl)imide.
  • the mass of the lithium salt accounts for 8-18% of the total mass of the electrolyte
  • a second aspect of the present invention provides a lithium secondary battery, which includes a positive electrode, a negative electrode, and the electrolyte.
  • the lithium secondary battery in the present invention is selected from any one of lithium ion batteries, lithium sulfur batteries, and lithium air batteries; lithium ion batteries, lithium sulfur batteries and lithium air batteries are technical terms well known to those skilled in the art.
  • the shape and type of the lithium secondary battery in the present invention are not particularly limited, and may be lithium secondary batteries such as lithium ion batteries, lithium ion polymer batteries, lithium sulfur batteries, and lithium primary batteries.
  • the lithium battery can be manufactured by a manufacturing method known in the related art.
  • the positive electrode contains a positive electrode active material capable of storing and releasing lithium.
  • the positive electrode active material is not particularly limited as long as it can electrochemically store and release lithium ions.
  • a substance containing lithium and at least one transition metal is preferable, and examples thereof include lithium-transition metal composite oxides and lithium-containing transition metal phosphate compounds.
  • the transition metal of the lithium-transition metal composite oxide V, Ti, Cr, Mn, Fe, Co, Ni, Cu, etc. are preferred, and specific examples include lithium-cobalt composite oxides such as LiCoO 2 ; lithium such as LiNiO 2 -Nickel composite oxide; LiMnO 2 , LiMn 2 O 4 , Li 2 MnO 3 and other lithium-manganese composite oxides; use Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg , Ga, Zr, Si and other metals instead of a part of the transition metal atoms forming the main body of these lithium-transition metal composite oxides.
  • lithium-cobalt composite oxides such as LiCoO 2 ; lithium such as LiNiO 2 -Nickel composite oxide; LiMnO 2 , LiMn 2 O 4 , Li 2 MnO 3 and other lithium-manganese composite oxides; use Al, Ti, V, Cr, Mn, Fe, Co
  • substances obtained by substitution include, for example, LiNi 0.5 Mn 0.5 O 2 , LiNi 0.85 Co 0.10 Al 0.05 O 2 , LiNi 0.33 Co 0.33 Mn 0.33 O 2 , LiMn 1.8 Al 0.2 O 4 , LiMn 1.5 Ni 0.5 O 4 etc.
  • the transition metal of the lithium-containing transition metal phosphate compound is preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu, etc.
  • LiFePO 4 , Li 3 Fe 2 (PO 4 ) 3 Iron phosphates such as LiFeP 2 O 7 ; Cobalt phosphates such as LiCoPO 4 ; Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si, etc.
  • the metal substitutes for a substance or the like obtained by substituting a part of the transition metal atom forming the main body of these lithium-containing transition metal phosphate compounds.
  • any one of Li 1+a (Ni x Co y M 1-xy )O 2 , Li(Ni n Mn m Co 2-nm )O 4 , and LiM p (PO 4 ) q is preferable; 0 ⁇ a ⁇ 0.3, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ x+y ⁇ 1, 0 ⁇ n ⁇ 2, 0 ⁇ m ⁇ 2, 0 ⁇ n+m ⁇ 2, M is selected from Al , Fe, Ni, Co, Mn, V, and 0 ⁇ p ⁇ 5, 0 ⁇ q ⁇ 5.
  • the binder used in the production of the positive electrode active material layer is not particularly limited. When the coating method is used, any material that can be dissolved or dispersed in the liquid medium used in the electrode production is sufficient. Specific examples include Polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, nitrocellulose and other resin polymers; SBR (styrene-butadiene rubber ), NBR (acrylonitrile-butadiene rubber), fluororubber, isoprene rubber, butadiene rubber, ethylene-propylene rubber and other rubbery polymers; styrene-butadiene-styrene block copolymer Or its hydrogenated product, EPDM (ethylene-propylene-diene terpolymer), styrene-ethylene-butadiene-ethylene copolymer, styrene-isoprene-styrene block copolymer or its addition Hydrogen compounds and other thermoplastic e
  • the ratio of the binder in the positive electrode active material layer is too low, the positive electrode active material cannot be sufficiently maintained, the mechanical strength of the positive electrode is insufficient, and battery performance such as cycle characteristics deteriorate. On the other hand, if the proportion of the binder is too high, it may sometimes cause a decrease in battery capacity or conductivity.
  • any solvent can be used as long as it can dissolve or disperse the positive electrode active material, conductive material, binder, and thickener used as required.
  • water-based solvents can be used. Any solvent among solvents and organic solvents.
  • aqueous medium water, a mixed medium of alcohol and water, etc. are mentioned.
  • organic solvents include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and methyl naphthalene; heterocyclic compounds such as quinoline and pyridine; acetone, methyl ethyl ketone, cyclohexanone, etc.
  • Ketones such as methyl acetate and methyl acrylate; amines such as diethylenetriamine and N,N-dimethylaminopropylamine; ethers such as ether, propylene oxide, and tetrahydrofuran (THF); N- Amides such as methylpyrrolidone (NMP), dimethylformamide and dimethylacetamide; polar aprotic solvents such as hexamethylphosphoramide and dimethylsulfoxide.
  • NMP methylpyrrolidone
  • NMP dimethylformamide and dimethylacetamide
  • polar aprotic solvents such as hexamethylphosphoramide and dimethylsulfoxide.
  • the positive electrode can be produced by forming a positive electrode active material layer containing a positive electrode active material and a binder on a current collector.
  • the production of the positive electrode using the positive electrode active material can be performed by a conventional method.
  • the positive electrode active material and the binder, as well as the conductive materials and thickeners used as needed can be dry-mixed and made into a sheet, and then the sheet material can be pressed on the positive current collector.
  • these materials are dissolved or dispersed in a liquid medium to prepare a slurry, and the slurry is coated on a positive electrode current collector and dried to form a positive electrode active material layer on the current collector to obtain a positive electrode.
  • the negative electrode contains a negative electrode active material capable of storing and releasing lithium.
  • a transition material selected from the group consisting of metallic lithium, lithium-containing alloys, metals or alloys capable of being alloyed with lithium, oxides capable of doping/undoping lithium ions, and transitions capable of doping/undoping lithium ions can be used. At least one combination of one or more of the metal nitride and the carbon material capable of doping/undoping lithium ions.
  • the negative electrode active material is preferably any one or a combination of lithium metal, lithium alloy, carbon material, silicon or tin and oxides thereof.
  • the binder for binding the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the solvent used in the production of the non-aqueous electrolyte and the electrode.
  • resins such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, polyimide, cellulose, and nitrocellulose.
  • Polymers SBR (styrene butadiene rubber), isoprene rubber, butadiene rubber, fluororubber, NBR (nitrile rubber), ethylene propylene rubber and other rubbery polymers; styrene-butadiene-styrene embedded Block copolymer or its hydrogenated product; EPDM (ethylene-propylene-diene terpolymer), styrene-ethylene-butadiene-styrene copolymer, styrene-isoprene-styrene block copolymer Thermoplastic elastomer-like polymers or its hydrogenated products; syndiotactic 1,2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymer, propy
  • any solvent that can dissolve or disperse the negative electrode active material, the binder, and the thickener and conductive material used as needed is not particularly limited, and it can be water-based Any solvent among solvents and non-aqueous solvents.
  • aqueous solvents examples include water, alcohol, etc.; examples of non-aqueous solvents include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, and acrylic acid.
  • NMP N-methylpyrrolidone
  • a thickener in the case of using an aqueous solvent, it is preferable to use a thickener while containing a dispersant and the like, and to form a slurry with a latex such as SBR.
  • a dispersant and the like it is preferable to use a thickener while containing a dispersant and the like, and to form a slurry with a latex such as SBR.
  • these solvents may be used singly, or two or more of them may be used in any combination and ratio.
  • Thickeners are usually used to adjust the viscosity of the slurry. There are no particular restrictions on the thickener, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, Their salt etc. These thickeners may be used alone, or two or more of them may be used in any combination and ratio.
  • the thickener When the thickener is in an appropriate range with respect to the negative electrode active material, the decrease in battery capacity and the increase in impedance can be suppressed, and good coating properties can be ensured.
  • the production of the negative electrode of the present invention can employ any known method.
  • a slurry can be prepared by adding a binder, a solvent, a thickener, a conductive material, etc. to the negative electrode active material, and then coating the slurry on the current collector and drying it. After that, pressing is performed to form electrodes.
  • Embodiment 1 of the present invention provides a lithium secondary battery, the preparation process of which is as follows:
  • the positive electrode active material, lithium nickel cobalt manganese oxide (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ), the conductive agent Super-P, and the binder PVDF are dissolved in the solvent N-form at a mass ratio of 96:2.0:2.0
  • the negative electrode active material graphite, conductive agent Super-P, thickener CMC, and binder SBR are dissolved in the solvent deionized water at a mass ratio of 96.5:1.0:1.0:1.5 to make a negative electrode slurry, and then the negative electrode slurry Coat evenly on the current collector copper foil with a coating amount of 0.0089g/cm 2 , then dry at 85°C, then perform cold pressing, trimming, cutting, and slitting, and then dry at 110°C under vacuum for 4h , Weld the tabs to make the negative electrode sheet of the lithium secondary battery that meets the requirements.
  • the electrolyte of the lithium secondary battery uses 12.5% of the total mass of the electrolyte as the lithium salt, and the mixture of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate as the non-aqueous organic solvent, accounting for 81.5 of the total mass of the electrolyte %, wherein the mass ratio of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate is 3:5:2.
  • the lithium secondary electrolyte also contains additives, and the additive is compound 1 which accounts for 3.0% of the total mass of the lithium secondary battery electrolyte.
  • the second additive is vinylene carbonate and 1,3-propane sultone, which respectively account for 1.0% and 2.0% of the total mass of the electrolyte.
  • the positive electrode sheet, the negative electrode sheet and the separator of the lithium secondary battery prepared according to the foregoing process are made into a cell with a thickness of 8mm, a width of 60mm, and a length of 130mm through a winding process, and vacuum-baked at 75°C for 10h, Inject electrolyte, let stand for 24h, then charge to 4.2V with a constant current of 0.1C (160mA), then charge at a constant voltage of 4.2V until the current drops to 0.05C (80mA), and then use a constant current of 0.1C (160mA) Discharge to 3.0V, repeat the charge and discharge twice, and finally charge to 3.8V with a constant current of 0.1C (160mA) to complete the preparation of the lithium secondary battery.
  • Embodiment 2 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the electrolyte of the lithium secondary battery uses 10.0% of the total mass of the electrolyte as lithium salt.
  • the non-aqueous organic solvent is ethylene carbonate and ethyl methyl carbonate, which account for 87.0% of the total mass of the electrolyte, and the mass ratio is 1:2.
  • Compound 2 is added, which accounts for 1.0% of the total mass of the electrolyte.
  • the second additive is lithium difluorophosphate, which accounts for 1.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiNi 0.8 Co 0.1 Mn 0.1 O 2 .
  • Embodiment 3 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the non-aqueous organic solvent is ethylene carbonate and ethyl methyl carbonate, which account for 83.0 of the total mass of the electrolyte. %, the mass ratio is 1:3. Compound 3 is added, which accounts for 1.0% of the total mass of the electrolyte.
  • the second additives are vinylene carbonate and fluoroethylene carbonate, which respectively account for 0.5% and 3.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiNi 0.8 Co 0.15 Al 0.05 O 2 .
  • Embodiment 4 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the non-aqueous organic solvent is ethylene carbonate and diethyl carbonate, which account for 84.0 of the total mass of the electrolyte. %, the mass ratio is 1:2. Compound 4 is added, which accounts for 2.5% of the total mass of the electrolyte.
  • the second additives are lithium difluorooxalate borate and fluoroethylene carbonate, which respectively account for 0.5% and 5.0% of the total mass of the electrolyte.
  • the positive electrode material used in the lithium secondary battery is LiCoO 2
  • the negative electrode material is a silicon-carbon composite material.
  • Embodiment 5 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the electrolyte of the lithium secondary battery uses 15% of the total mass of the electrolyte as lithium salt.
  • Non-aqueous organic solvents are ethylene carbonate, propylene carbonate, and diethyl carbonate, accounting for 81.5% of the total mass of the electrolyte, and the mass ratio is 4:1:5.
  • Compound 5 is added, which accounts for 1.0% of the total mass of the electrolyte.
  • the second additives are vinylene carbonate and tripropynyl phosphate, which respectively account for 0.5% and 2.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiNi 0.8 Co 0.15 Al 0.05 O 2
  • the anode material is lithium titanate.
  • the charge cut-off voltage of the lithium secondary battery is 2.7V.
  • Embodiment 6 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the mixture of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate is non-aqueous organic
  • the solvent accounts for 83.5% of the total mass of the electrolyte, and the mass ratio is 3:5:2.
  • Compound 6 is added, which accounts for 0.5% of the total mass of the electrolyte.
  • the second additives are triallyl phosphate and fluoroethylene carbonate, which respectively account for 1.0% and 3.0% of the total mass of the electrolyte.
  • the cathode material used in lithium secondary batteries is LiCoO 2 .
  • Embodiment 7 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the electrolyte of the lithium secondary battery uses 17.5% of the total mass of the electrolyte as lithium salt.
  • the electrolyte of the lithium secondary battery uses 17.5% of the total mass of the electrolyte as lithium salt.
  • the second additive is lithium difluorophosphate, which accounts for 0.5% of the total mass of the electrolyte.
  • the positive electrode material used in the lithium secondary battery is LiMn 2 O 4
  • the negative electrode material is lithium titanate. .
  • Embodiment 8 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the mixture of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate is non-aqueous organic
  • the solvent accounts for 83.5% of the total mass of the electrolyte, the mass ratio is 3:5:2, and the compound 8 is added, which accounts for 1.0% of the total mass of the electrolyte.
  • the second additives are triallyl isocyanurate and lithium difluorophosphate, which respectively account for 0.5% and 3.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiMnO 2 .
  • Example 9 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 1, except that the electrolyte of the lithium secondary battery uses 15% of the total mass of the electrolyte as lithium salt.
  • Non-aqueous organic solvents are ethylene carbonate, propylene carbonate, and diethyl carbonate, accounting for 77.5% of the total mass of the electrolyte, and the mass ratio is 4:1:5.
  • Compound 9 is added, which accounts for 5.0% of the total mass of the electrolyte.
  • the second additives are vinylene carbonate and tripropynyl phosphate, which respectively account for 0.5% and 2.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiNi 0.8 Co 0.15 Al 0.05 O 2
  • the anode material is lithium titanate.
  • the charge cut-off voltage of the lithium secondary battery is 2.7V.
  • Embodiment 10 of the present invention provides a lithium secondary battery, which is prepared according to the method of Embodiment 2, except that the second additive is not added.
  • Embodiment 11 of the present invention provides a lithium secondary battery.
  • the lithium secondary battery is prepared according to the method of embodiment 1, except that the electrolyte of the lithium secondary battery uses 15% of the total mass of the electrolyte.
  • the imide lithium is a lithium salt
  • the non-aqueous organic solvent is ethylene carbonate, ethyl acetate, and diethyl carbonate, accounting for 81.5% of the total mass of the electrolyte, and the mass ratio is 4:1:5.
  • Compound 11 is added, which accounts for 1.0% of the total mass of the electrolyte.
  • the second additives are triallyl phosphate and methylene disulfonate, which respectively account for 0.5% and 2.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiNi0.8Co0.15Al0.05O2, and the anode material is lithium titanate.
  • the charge cut-off voltage of the lithium secondary battery is 2.7V.
  • Embodiment 12 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that ethylene carbonate, ethyl methyl carbonate, methyl propionate, 2,2-di
  • the mixture of fluoroethyl ethyl acetate is a non-aqueous organic solvent, accounting for 83.5% of the total mass of the electrolyte, and the mass ratio is 3:4:2:1.
  • Compound 13 is added, which accounts for 0.5% of the total mass of the electrolyte.
  • the second additives are lithium dioxalate borate and tris(trimethylsilyl) phosphate, which respectively account for 1.0% and 3.0% of the total mass of the electrolyte.
  • the cathode material used in lithium secondary batteries is LiCoO2.
  • Embodiment 13 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the electrolyte of the lithium secondary battery uses 17.5% of the total mass of the electrolyte.
  • Lithium imide is a lithium salt, and a mixture of ethylene carbonate, ethyl methyl carbonate, and propyl propionate is a non-aqueous organic solvent, accounting for 78.0% of the total mass of the electrolyte, and the mass ratio is 3:5:2, and compound 15 is added , Accounting for 4.0% of the total mass of the electrolyte.
  • the second additive is tris(trimethylsilyl) borate, which accounts for 0.5% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiMn2O4, and the anode material is lithium titanate.
  • Comparative Example 1 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 1, except that Compound 1 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 2 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 2, except that Compound 2 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 3 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 3, except that Compound 3 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 4 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 4, except that Compound 4 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 5 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 5, except that Compound 5 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 6 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 6, except that Compound 6 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 7 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 7 except that Compound 7 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 8 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 8 except that Compound 8 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 9 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 9 except that Compound 9 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 10 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 1 except that Compound 10 is added to the electrolyte of the lithium secondary battery.
  • Comparative Example 11 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 11, except that Compound 12 is added to the electrolyte of the lithium secondary battery.
  • Comparative Example 12 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 12, except that Compound 14 is added to the electrolyte of the lithium secondary battery.
  • Comparative Example 13 of the present invention provides a lithium secondary battery.
  • the lithium secondary battery is prepared according to the method of Example 13, except that compound 16 is added to the electrolyte of the lithium secondary battery.
  • Cycle experiment test the internal resistance of the batteries obtained in Comparative Examples 1-13 and Examples 1-13 at room temperature 25°C; charge and discharge at a rate of 2CC/0.5CD at 25°C; at a low temperature of -10 Charge and discharge at a rate of 0.5CC/0.2CD at °C; charge and discharge cycle test at a rate of 0.5CC/0.5CD at a high temperature of 55°C, record the last cycle discharge capacity and divide by the first cycle discharge respectively The capacity is the capacity retention rate, and the recorded results are shown in Table 1.
  • the sulfonate compound can significantly reduce the internal resistance of the battery, and the battery's low-temperature cycle, high-rate normal-temperature cycle, high-temperature cycle, and high-temperature storage expansion are all significantly improved.
  • Examples 1-13 are significantly better than the comparative examples.
  • the results of Example 10 show that without the second additive, the battery also has very low internal resistance, good low-temperature cycling, high-rate normal-temperature cycling, and high-temperature cycling. Circulation, and significantly inhibit the expansion after high temperature storage. Therefore, the battery prepared by using the electrolyte of the present invention can obtain lower internal resistance, better low temperature cycle, large rate normal temperature cycle, high temperature cycle, and lower high temperature storage expansion.

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Abstract

L'invention appartient au domaine technique des batteries secondaires au lithium-ion et concerne en particulier un électrolyte de batterie secondaire au lithium-ion servant à réduire la résistance de batterie et une batterie secondaire au lithium-ion. Selon un premier aspect de l'invention, l'électrolyte de la batterie secondaire au lithium-ion comprend un solvant non aqueux, un sel de lithium et un additif, l'additif contenant un composé de sulfonate. L'électrolyte de batterie secondaire au lithium-ion et la batterie secondaire au lithium-ion selon l'invention présentent une résistance réduite, ainsi qu'une performance à basse température, une performance à haute température et une durée de vie améliorées.
PCT/CN2019/127033 2019-06-12 2019-12-20 Électrolyte de batterie secondaire au lithium-ion pour réduire la résistance de batterie et batterie secondaire au lithium-ion correspondante WO2020248567A1 (fr)

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EP19933122.4A EP3972024A4 (fr) 2019-06-12 2019-12-20 Électrolyte de batterie secondaire au lithium-ion pour réduire la résistance de batterie et batterie secondaire au lithium-ion correspondante
US17/614,215 US20220238909A1 (en) 2019-06-12 2019-12-20 Secondary lithium-ion battery electrolyte solution for reducing battery resistance and secondary lithium-ion battery thereof

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CN112928329A (zh) * 2021-02-18 2021-06-08 湖州昆仑亿恩科电池材料有限公司 一种锂离子电池电解液添加剂及其制备方法和应用
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